WO2020158751A1 - 共役ジエン系重合体の製造方法 - Google Patents

共役ジエン系重合体の製造方法 Download PDF

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WO2020158751A1
WO2020158751A1 PCT/JP2020/003031 JP2020003031W WO2020158751A1 WO 2020158751 A1 WO2020158751 A1 WO 2020158751A1 JP 2020003031 W JP2020003031 W JP 2020003031W WO 2020158751 A1 WO2020158751 A1 WO 2020158751A1
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Prior art keywords
ethanol
gas
derived
alcohol
butadiene
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PCT/JP2020/003031
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English (en)
French (fr)
Japanese (ja)
Inventor
心 濱地
宣利 柳橋
悠 西山
和都 夏山
Original Assignee
積水化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority claimed from JP2019012568A external-priority patent/JP7149864B2/ja
Priority claimed from JP2019012564A external-priority patent/JP7339737B2/ja
Priority claimed from JP2019050436A external-priority patent/JP7339749B2/ja
Priority claimed from JP2019050489A external-priority patent/JP7339751B2/ja
Priority claimed from JP2019050480A external-priority patent/JP7323307B2/ja
Priority claimed from JP2019050474A external-priority patent/JP7323306B2/ja
Priority claimed from JP2019050484A external-priority patent/JP7339750B2/ja
Priority claimed from JP2019050472A external-priority patent/JP7323305B2/ja
Priority claimed from JP2019117745A external-priority patent/JP2021004190A/ja
Priority claimed from JP2019117749A external-priority patent/JP2021004191A/ja
Priority claimed from JP2019117754A external-priority patent/JP2021004192A/ja
Priority claimed from JP2019117720A external-priority patent/JP2021004189A/ja
Priority to US17/297,770 priority Critical patent/US20210395421A1/en
Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社
Priority to EP20749153.1A priority patent/EP3770186B1/de
Priority to CN202080009613.5A priority patent/CN113348184B/zh
Publication of WO2020158751A1 publication Critical patent/WO2020158751A1/ja

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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1665—Conversion of synthesis gas to chemicals to alcohols, e.g. methanol or ethanol
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/26—Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • C12R2001/145—Clostridium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Definitions

  • Japanese Patent Application 2019-050465, Japanese Patent Application 2019-050472, Japanese Patent Application 2019-050474, Japanese Patent Application 2019-050480, Japanese Patent Application 2019-050484, and Japanese Patent Application No. 2019-050489 Japanese Patent Application No. 2019-117720 filed on June 25, 2019, Japanese Patent Application No. 2019-117745, Japanese Patent Application No. 2019-17749, and Japanese Patent Application 2019- No. 117754, as well as Japanese Patent Application No. 2019-126455 filed on Jul. 5, 2019, the entire disclosures of which are incorporated herein by reference. Be part of.
  • the present invention relates to a method for producing a conjugated diene polymer. More specifically, the present invention relates to a method for producing a non-petrification-derived conjugated diene-based polymer by using a non-petrification-source alcohol derived from a non-petrification source, such as ethanol, in which the content of a specific trace component is adjusted.
  • a non-petrification-source alcohol derived from a non-petrification source such as ethanol
  • non-edible raw materials that have been discarded in the past.
  • a method of producing alcohols by a fermentation method using a waste material or a cellulose derived from waste paper as a non-edible raw material, or gasifying a biomass raw material as described above, and using a catalyst from synthesis gas to produce alcohol Although a method for producing the same has been proposed, it has not yet been put into practical use. Further, even if various petrochemical products can be produced from these decalcified raw materials, they will eventually become waste plastics that do not decompose naturally, so they cannot be said to be effective as a drastic solution to environmental problems. ..
  • Patent Documents 1 and 2 and the like disclose a technique of producing synthetic gas (gas containing CO and H 2 as main components) from waste and producing ethanol from the synthetic gas by a fermentation method. There is.
  • Patent Document 4 proposes to increase the ratio of natural rubber as a rubber component.
  • Patent Document 5 proposes to use a modified natural rubber as a rubber component.
  • Patent Document 6 proposes to use renewable (biological resource-derived) butadiene or isoprene as butadiene or isoprene which is a raw material of a rubber component.
  • Patent Documents 7 and 8 propose to synthesize 1,3-butadiene from commercially available bioethanol.
  • a conventional C2 raw material represented by ethanol is known to be a starting raw material for various chemical products, but as described above, it does not depend on petroleum resources or biomass resources.
  • Alcohol produced from resources was found to contain various trace amounts of unknown substances, unlike chemical raw materials derived from naphtha.
  • the characteristics of substances are unknown, and it has not been sufficiently studied in the past whether all substances should be removed or only specific substances should be removed. Therefore, even if an alcohol produced from a recycling resource is proposed in the above patent document, there is still room for technical improvement in order to put the alcohol into practical use.
  • the present invention has been made in view of such background art, and an object thereof is to provide a practical novel alcohol and its derivative which are more industrially valuable than existing petrochemical raw materials.
  • Patent Document 6 describes the use of alcohol obtained by fermenting biomass-derived sugars as a starting material in a method for producing renewable butadiene.
  • Patent Documents 7 and 8 propose to synthesize 1,3-butadiene from commercially available bioethanol.
  • commercially available alcohols described in known documents or equivalents are not intended specifically for practical chemical products, and various practical products (for example, , It was necessary to develop a raw material alcohol that can withstand the physical properties and characteristics of the resin and products using the resin. Therefore, there has been a demand for a wider technique for optimizing the scope of application of alcohol.
  • the present inventors have identified a wide variety of trace substances contained in alcohol produced from recyclable resources, and further determined the content by a novel production method. It was found that it was possible to control within a specific range, and in addition, various derivatives thereof exhibited superior effects compared with existing alcohols. For example, in the process of synthesizing butadiene from ethanol, the butadiene selectivity is improved as compared with the case of using conventional ethanol, and chemicals derived from alcohol at a practical level equivalent to or higher than existing alcohols or those The inventors have found that the products used can be obtained, and completed the present invention.
  • the present inventors have used, as a starting material, an alcohol such as the above non-petrified raw material-derived ethanol having a content of iron within a specific range, butadiene, etc. It has been found that a suitable rubber composition for a tire can be obtained by producing the conjugated diene-based polymer of No. 3, and further polymerizing the conjugated diene-based polymer to produce a non-petrification-derived conjugated diene-based polymer. The present invention is also based on such findings.
  • the present invention includes the following points.
  • a method for producing a non-petrification-derived conjugated diene polymer using a non-petrification-source alcohol as a raw material A non-petrified raw material-derived alcohol having an iron content of 0.0001 mg/L or more and 2 mg/L or less is used as a raw material, and the alcohol is brought into contact with the catalyst and heated to give a conjugate having a carbon number of C 4 to C 12.
  • a process for producing a diene Polymerizing a monomer containing the conjugated diene to produce a non-petrification derived conjugated diene polymer.
  • the conjugated diene is 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene,
  • the aromatic hydrocarbon is styrene, methylstyrene, ethylstyrene, t-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene, chlorostyrene, bromostyrene, methoxystyrene, dimethylaminomethylstyrene.
  • a method for producing a crosslinked rubber comprising: A method comprising the step of kneading the non-petrification-derived conjugated diene polymer obtained by the method according to any one of [1] to [9] as a rubber component and a filler to carry out crosslinking.
  • an alcohol having a very low content of a specific metal element preferably ethanol
  • various different effects can be obtained as compared with a commercially available industrial alcohol.
  • the butadiene selectivity in synthesizing butadiene using ethanol as a raw material is improved, the yield in synthesizing SBR is improved, the glass transition temperature of SBR is controlled, and butadiene/styrene is controlled. Percentage control is possible.
  • it is expected that the same effect can be obtained by adjusting the content of a specific metal element to an extremely low content.
  • the alcohol used in the present invention preferably ethanol is, for example, butadiene, ethylene, propylene, isobutene, acetaldehyde, acetic acid, ethyl acetate, methyl (meth)acrylate, ethyl-t-butyl ether ethylene glycol, ester composition, polyester.
  • the alcohol used in the present invention is cosmetics, perfume, fuel, antifreeze, bactericide, disinfectant, cleaning agent, mildew remover, detergent, hair wash, soap, antiperspirant, face wash sheet, solvent, paint, adhesive. It can be used for various uses of chemical products such as, diluents and food additives.
  • alcohol refers to a compound in which a hydrogen atom of hydrocarbon is replaced with a hydroxy group (—OH).
  • examples of the lower alcohol include methanol (methyl alcohol), ethanol (ethyl alcohol), 2-propanol, ethylene glycol, glycerin, phenol and the like, and preferably ethanol.
  • the higher alcohol usually has 8 to 22 carbon atoms, and specific examples thereof include capryl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol (cetanol), stearyl alcohol, oleyl alcohol, and linoleyl alcohol.
  • ethanol does not mean pure ethanol (a chemical formula: ethanol represented by CH 3 CH 2 OH) as a compound, and ethanol produced through synthesis or purification may be water or unavoidable. It means a composition containing impurities (contaminant components) that are included in the composition.
  • the content of each component such as an inorganic component and an organic component in the alcohol raw material is the amount (mg) of each component with respect to 1 L of alcohol.
  • a non-petrification raw material-derived alcohol having a controlled Fe (iron) content is used.
  • the content of Fe (iron) is 0.0001 mg/L or more and 2 mg/L or less, preferably 0.0005 mg/L or more, and more preferably 0.001 mg/L with respect to the alcohol.
  • the Fe content is the Fe element equivalent amount of the Fe compound.
  • the butadiene selectivity particularly when butadiene is synthesized from ethanol as a raw material is improved, the yield when SBR is synthesized is improved, and the glass transition temperature of SBR is increased. And the butadiene/styrene ratio can be controlled.
  • the iron content in alcohol can be measured by a conventionally known method.
  • a method of measuring the iron content for example, there is a method of analysis using an inductively coupled plasma mass spectrometer (Inductively Coupled Plasma Mass Spectrometry: ICP-MS).
  • ICP-MS Inductively Coupled Plasma Mass Spectrometry: ICP-MS, a standard curve for atomic absorption is analyzed after concentration adjustment to prepare a calibration curve, and the iron content is determined by analyzing the sample to be measured based on this calibration curve. Is.
  • the alcohol used in the present invention is not particularly limited, but is produced by using an alcohol having a gas containing carbon monoxide and hydrogen as a substrate, a microbial fermentation or a metal catalyst using sugar or cellulose as a raw material. It is preferably alcohol. With these alcohols, it is easy to adjust the iron content to the above concentration in the manufacturing process. Further, in general, commercially available non-fossil fuel-derived materials such as sugar ethanol, particularly ethanol for reagent on a small scale as described in known literatures may not contain Fe as described in Comparative Examples. all right. Therefore, for the purpose of industrial use as a chemical raw material, it becomes necessary to strictly control the Fe content.
  • the iron content may be adjusted to the above concentration by further purification, preferably the purification method described herein. If iron is not contained in excess of the above concentration, it may be contained until the step of producing ethanol from the raw material and/or the step of converting ethanol into a conjugated diene, and the timing of inclusion is not particularly limited. , Storage, transportation and delivery are also included.
  • the method of incorporating is not particularly limited, but may be, for example, addition or elution by contact with a metal containing Fe.
  • the butadiene selectivity in synthesizing butadiene from ethanol as a raw material is improved. It is possible to improve the yield in synthesizing SBR, control the glass transition temperature of SBR, and control the butadiene/styrene ratio.
  • the alcohol used in the present invention may contain an inorganic component other than Fe.
  • it may contain an inorganic component such as Si, K, or Na.
  • the compound containing these elements may be an inorganic compound or an organometallic compound.
  • the content of Si is preferably 10 mg/L or more, more preferably 20 mg/L or more, still more preferably 30 mg/L or more with respect to ethanol. In addition, it is preferably 100 mg/L or less, more preferably 90 mg/L or less, and further preferably 80 mg/L or less.
  • the Si content is the Si element equivalent amount of the Si compound.
  • the content of Si in alcohol, especially ethanol can be measured by a conventionally known method.
  • a method of measuring the Si content for example, a method of using an inductively coupled plasma mass spectrometer (Inductively Coupled Plasma Mass Spectrometry: ICP-MS) can be mentioned.
  • ICP-MS Inductively Coupled Plasma Mass Spectrometry: ICP-MS, a standard curve for atomic absorption is analyzed after concentration adjustment to prepare a calibration curve, and a sample to be measured is analyzed based on this calibration curve to determine the Si content. Is.
  • the alcohol of the present invention in particular ethanol, is obtained by extracting an ethanol-containing liquid obtained from a microbial fermenter as described later and further purifying it, but it contains other components in addition to the above-mentioned unavoidable substances. It may be.
  • a slight amount of aromatic compound may be contained.
  • the aromatic compound include toluene, ethylbenzene, o-xylene, m-xylene, and p-xylene, and one kind thereof may be contained or two or more kinds may be contained.
  • Ethylbenzene is preferably contained as the aromatic compound.
  • the content (total) of aromatic compounds contained in alcohol, particularly ethanol is preferably 0.4 mg/L or more, more preferably 0.5 mg/L or more, and further preferably, based on the whole ethanol. Is 0.7 mg/L or more, more preferably 1.0 mg/L or more, preferably 10 mg/L or less, more preferably 7 mg/L or less, and further preferably 5 mg/L or less. And even more preferably 3 mg/L or less.
  • the content of the aromatic compound is within the above numerical range, the styrene and ethanol are smoothly mixed during the polymerization reaction, and the yield of the polymerization reaction is improved.
  • the content of aromatic compounds in alcohol, especially ethanol can be measured by a conventionally known method.
  • a method of measuring the content of the aromatic compound for example, a method of analysis using gas chromatograph mass spectrometry (GC-MS) can be mentioned.
  • GC-MS gas chromatograph mass spectrometry
  • a standard gas is analyzed to prepare a calibration curve, and the sample to be measured is analyzed based on this calibration curve to determine the content of the aromatic compound.
  • the content of ethylbenzene is preferably 0.1 mg/L or more, more preferably 0.2 mg/L or more, and further preferably, based on the whole ethanol. It is 0.3 mg/L or more, further preferably 0.5 mg/L or more, preferably 5 mg/L or less, more preferably 3 mg/L or less, and further preferably 2 mg/L or less. And even more preferably 1 mg/L or less.
  • the content of ethylbenzene is within the above numerical range, styrene and ethanol are smoothly mixed during the polymerization reaction, and the yield of the polymerization reaction is improved.
  • the content of ethylbenzene in alcohol, especially ethanol can be measured by a conventionally known method.
  • Examples of the method for measuring the content of ethylbenzene include a method of analysis using gas chromatograph mass spectrometry (GC-MS).
  • GC-MS gas chromatograph mass spectrometry
  • a standard gas is analyzed to prepare a calibration curve, and a sample to be measured is analyzed based on this calibration curve to obtain the content of ethylbenzene.
  • the content of toluene is preferably 0.01 mg/L or more, more preferably 0.02 mg/L or more, and further preferably, based on the whole ethanol. 0.03 mg/L or more, still more preferably 0.05 mg/L or more, preferably 1 mg/L or less, more preferably 0.5 mg/L or less, still more preferably 0. It is 2 mg/L or less, and even more preferably 0.1 mg/L or less.
  • the content of toluene is within the above numerical range, styrene and ethanol are smoothly mixed during the polymerization reaction, and the yield of the polymerization reaction is improved.
  • the content of toluene in ethanol can be measured by a conventionally known method.
  • a method of measuring the content of toluene for example, a method of analysis using gas chromatograph mass spectrometry (GC-MS) can be mentioned.
  • GC-MS gas chromatograph mass spectrometry
  • a standard gas is analyzed to prepare a calibration curve, and a sample to be measured is analyzed based on this calibration curve to obtain the content of toluene.
  • the content of o-xylene is preferably 0.1 mg/L or more, and more preferably 0.2 mg/L or more, based on the whole ethanol. , More preferably 0.3 mg/L or more, even more preferably 0.5 mg/L or more, preferably 5 mg/L or less, more preferably 3 mg/L or less, and further preferably It is 2 mg/L or less, and even more preferably 1 mg/L or less.
  • the content of o-xylene is within the above numerical range, styrene and ethanol are smoothly mixed during the polymerization reaction, and the yield of the polymerization reaction is improved.
  • the content of o-xylene in alcohol, especially ethanol can be measured by a conventionally known method.
  • a method for measuring the o-xylene content for example, a method of analyzing using gas chromatograph mass spectrometry (GC-MS) can be mentioned.
  • GC-MS gas chromatograph mass spectrometry
  • a standard gas is analyzed to prepare a calibration curve, and a sample to be measured is analyzed based on this calibration curve to determine the content of o-xylene.
  • the content (total) of m-xylene and/or p-xylene is preferably 0.1 mg/L based on the whole ethanol. Or more, more preferably 0.2 mg/L or more, preferably 5 mg/L or less, more preferably 3 mg/L or less, even more preferably 2 mg/L or less, and even more preferably Is 1 mg/L or less.
  • the content of m-xylene and/or p-xylene is within the above numerical range, the mixing of styrene and ethanol becomes smooth during the polymerization reaction, and the yield of the polymerization reaction improves.
  • the content of m or p-xylene in alcohol, especially ethanol can be measured by a conventionally known method.
  • Examples of the method for measuring the content of m or p-xylene include a method of analysis using gas chromatograph mass spectrometry (GC-MS). In the method of analysis using GC-MS, a standard gas is analyzed to prepare a calibration curve, and a sample to be measured is analyzed based on this calibration curve to determine the content of m or p-xylene. ..
  • the chlorine is contained in alcohol, especially ethanol, it is preferably less than 2 mg/L. If chlorine is mixed in the above numerical range, the catalyst of the reaction for synthesizing butadiene from ethanol will be deactivated and the conversion rate of ethanol will decrease.
  • the content of chlorine in alcohol, especially ethanol can be measured by a conventionally known method.
  • Examples of the method for measuring the content of chlorine include a method of analysis using ion chromatography. In the method of analysis using ion chromatography, a standard solution is analyzed to create a calibration curve, and a sample to be measured is analyzed based on this calibration curve to obtain the chlorine content.
  • the alcohol of the present invention contains the above-mentioned inorganic components and, if desired, a trace amount of organic components such as aromatic hydrocarbons and aliphatic hydrocarbons, but the main component of ethanol is ethanol.
  • the concentration of (pure ethanol as a compound) is 75% by volume or more, preferably 80% by volume or more, more preferably 90% by volume or more, further preferably 95% by volume or more, and further more preferably, based on the whole ethanol. Is 98% by volume or more, preferably 99.999% by volume or less, more preferably 99.99% by volume or less, still more preferably 99.9% by volume or less, still more preferably 99.5% by volume or less. is there.
  • the method for producing an alcohol having a specific inorganic/organic compound as described above, particularly ethanol is not particularly limited as long as it is within the content range specified in the present invention.
  • Biomass resources specifically, for example, cellulosic plants (pulp, waste paper, papermaking, etc.), wood, charcoal, compost, natural rubber, cotton, sugarcane, okara, oils and fats, plants (corn, cassava, bagasse, etc.), Examples include marine product residues, livestock excrement, waste, algae, and the like.
  • the biomass resources may be those extracted and purified from the above-mentioned biomass resources or the above-treated biomass resources (that is, biomass-derived substances).
  • sugar ethanol purified from these biomass resources may be used.
  • ethanol can be produced by microbial fermentation of synthetic gas containing carbon monoxide derived from waste or exhaust gas.
  • the content of the aromatic compound or the like in the raw material gas derived from the waste or the exhaust gas and the refining conditions may be controlled to control the amount of the aromatic compound or the like contained in the final product.
  • a method for producing ethanol by microbial fermentation of synthetic gas containing carbon monoxide derived from waste or exhaust gas will be described.
  • the method for producing alcohol, in particular ethanol comprises a step of converting a carbon source into a synthesis gas containing carbon monoxide and hydrogen, and supplying the synthesis gas containing carbon monoxide and hydrogen to a microbial fermentation tank to carry out microbial fermentation to obtain an ethanol-containing liquid.
  • a microbial fermentation step for obtaining a separation step of separating the ethanol-containing liquid into a liquid or solid component containing microorganisms and a gas component containing ethanol, a liquefaction step of condensing and liquefying the gas component, and a liquefaction step.
  • a purification step of purifying ethanol from the obtained liquid substance is included as a step, but a raw material gas generation step, a synthesis gas preparation step, a wastewater treatment step, etc. may be included as necessary.
  • each step will be described.
  • the raw material gas production step is a step of producing a raw material gas by gasifying a carbon source in the gasification section.
  • a gasification furnace may be used in the raw material gas generation step.
  • the gasification furnace is a furnace for burning a carbon source (incomplete combustion), and examples thereof include a shaft furnace, a kiln furnace, a fluidized bed furnace, and a gasification reforming furnace.
  • the gasification furnace is preferably a fluidized bed furnace type because a high hearth load and excellent operability can be achieved by partially burning the waste.
  • the waste is gasified in a fluidized-bed furnace at low temperature (about 450-600°C) and low oxygen atmosphere, and decomposed into gas (carbon monoxide, carbon dioxide, hydrogen, methane, etc.) and carbon-rich char. To do. Furthermore, since the incombustibles contained in the waste are separated from the furnace bottom in a sanitary and low-oxidation state, it is possible to selectively recover valuable substances such as iron and aluminum in the incombustibles. Therefore, gasification of such waste enables efficient resource recycling.
  • the gasification temperature in the raw material gas production step is not particularly limited, but is usually 100 to 2500°C, preferably 200 to 2100°C.
  • the reaction time for gasification in the raw material gas generation step is usually 2 seconds or longer, preferably 5 seconds or longer.
  • the carbon source used in the raw material gas generation process is not particularly limited, and examples thereof include a coke oven in a steel mill, a blast furnace (blast furnace gas), coal used in a converter or a coal-fired power plant, an incinerator (especially a gasification furnace).
  • Various carbon-containing materials can be suitably used for the purpose of recycling, such as general waste and industrial waste introduced into, and carbon dioxide by-produced by various industries.
  • the carbon source is preferably waste, and specifically, plastic waste, garbage, municipal solid waste (MSW), industrial solid waste, waste tires, biomass waste, futon.
  • Household waste such as paper and paper, waste such as building materials, coal, petroleum, compounds derived from petroleum, natural gas, shale gas, and the like.
  • various wastes are preferable, from the viewpoint of separation cost, unsorted Municipal solid waste is more preferred.
  • the carbon source is, for example, the use of waste tires as a combustion material, specifically, a gas generated when the waste tires are thermally burned and thermal energy generated at that time is recovered, such as thermal recycling. Can also be used.
  • the apparatus for burning is not particularly limited, and examples thereof include the above-described blast furnace of a steel mill, blast furnace (blast furnace gas), coal used in converters and coal-fired power plants, incinerators, boilers, and the like.
  • blast furnace gas blast furnace gas
  • coal used in converters and coal-fired power plants incinerators, boilers, and the like.
  • about 60% of the raw materials of tires are suitable for combustion materials, and tire chips obtained from waste tires have a total calorific value of 35,000 kJ per kg, so they are almost the same as petroleum products such as light oil and heavy oil. Therefore, it is suitable as an alternative fuel such as coal.
  • CO 2 is the main gas
  • the gas generated by these is converted into CO by using a known technique and used to achieve resource recycling recycling as an effective effect measure
  • the raw material gas obtained by gasifying the carbon source contains carbon monoxide and hydrogen as essential components, but may further contain carbon dioxide, oxygen, and nitrogen. As other components, the raw material gas may further contain components such as soot, tar, nitrogen compounds, sulfur compounds, phosphorus compounds and aromatic compounds.
  • the raw material gas is subjected to a heat treatment (commonly called gasification) for burning (incompletely burning) the carbon source, that is, by partially oxidizing the carbon source, so that carbon monoxide is
  • a heat treatment commonly called gasification
  • the carbon source that is, by partially oxidizing the carbon source, so that carbon monoxide is
  • it may be produced as a gas containing 0.1 vol% or more, preferably 10 vol% or more, more preferably 20 vol% or more.
  • the synthesis gas purification step is a step of removing or reducing specific substances such as various pollutants, dust particles, impurities, and undesired amounts of compounds from the raw material gas.
  • the source gas is usually 0.1 vol% or more and 80 vol% or less of carbon monoxide, 0.1 vol% or more and 70 vol% or less of carbon dioxide, and 0% or less of hydrogen. 1% by volume or more and 80% by volume or less, further containing 1 mg/L or more of nitrogen compounds, 1 mg/L or more of sulfur compounds, 0.1 mg/L or more of phosphorus compounds, and/or 10 mg/L or more of aromatic compounds.
  • the pressure swing adsorption device filled with the above-mentioned regenerated adsorbent is used to adsorb carbon dioxide gas in the syngas to the regenerated adsorbent (zeolite), and the carbon dioxide gas concentration in the syngas is increased.
  • the synthesis gas may be subjected to other conventionally known processing steps to remove impurities and adjust the gas composition.
  • Other processing steps include, for example, a gas chiller (water separator), a low temperature separator (deep cooling separator), a cyclone, a particle (soot) separator such as a bag filter, and a scrubber (water-soluble impurity separator).
  • the treatment can be carried out using one or more of a device (PTSA), a separation device using activated carbon, a deoxygenation catalyst, specifically, a separation device using a copper catalyst or a palladium catalyst.
  • a device PTSA
  • a separation device using activated carbon PTSA
  • a deoxygenation catalyst specifically, a separation device using a copper catalyst or a palladium catalyst.
  • the concentrations of iron and chromium derived from the raw material gas can be controlled by adjusting the conditions of the above processing steps. For example, by adjusting conditions such as the residence time of the scrubber and membrane separation, these concentrations can be reduced below the detection limit. By reducing the concentrations of iron and chromium in the raw material gas in this way, the content of iron and chromium in the final alcohol, especially ethanol, can be reduced to below the detection limit.
  • the synthesis gas used in the method for producing alcohol of the present invention contains at least carbon monoxide as an essential component, and may further contain hydrogen, carbon dioxide, and nitrogen.
  • the synthesis gas used in the present invention produces a raw material gas by gasifying a carbon source (raw material gas producing step), and then adjusts the concentration of each component of carbon monoxide, carbon dioxide, hydrogen and nitrogen from the raw material gas.
  • the gas obtained through the steps of reducing or removing the substances and compounds as described above may be used as the synthesis gas.
  • the carbon monoxide concentration in the synthesis gas is usually 20% by volume or more and 80% by volume or less, preferably 25% by volume or more and 50% by volume, based on the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas. It is not more than 35% by volume, and more preferably not less than 35% by volume and not more than 45% by volume.
  • the hydrogen concentration in the synthesis gas is usually 10% by volume or more and 80% by volume or less, preferably 30% by volume or more and 55% by volume, with respect to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas. It is below, and more preferably from 40% by volume to 50% by volume.
  • the carbon dioxide concentration in the synthesis gas is usually 0.1% by volume or more and 40% by volume or less, preferably 0.3% by volume or more with respect to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas. It is 30 volume% or less, more preferably 0.5 volume% or more and 10 volume% or less, and particularly preferably 1 volume% or more and 6 volume% or less.
  • the nitrogen concentration in the synthesis gas is usually 40% by volume or less, preferably 1% by volume or more and 20% by volume or less, with respect to the total concentration of carbon monoxide, carbon dioxide, hydrogen and nitrogen in the synthesis gas. It is more preferably 5% by volume or more and 15% by volume or less.
  • Concentrations of carbon monoxide, carbon dioxide, hydrogen and nitrogen can be changed by changing the elemental composition of hydrocarbons (carbon and hydrogen) and nitrogen of the carbon source in the raw material gas production process, combustion temperature and oxygen concentration of the supply gas during combustion.
  • the combustion conditions such as the above, it is possible to obtain a predetermined range. For example, if you want to change the concentration of carbon monoxide or hydrogen, change to a carbon source that has a high ratio of hydrocarbons (carbon and hydrogen) such as waste plastic, and if you want to reduce the nitrogen concentration, you need to change the oxygen concentration in the source gas generation process.
  • the synthesis gas used in the present invention is not particularly limited in addition to the above-mentioned components, but may contain a sulfur compound, a phosphorus compound, a nitrogen compound and the like.
  • the content of each of these compounds is preferably 0.05 mg/L or more, more preferably 0.1 mg/L or more, still more preferably 0.5 mg/L or more, and preferably 2000 mg/L or less, It is more preferably 1000 mg/L or less, still more preferably 80 mg/L or less, even more preferably 60 mg/L or less, and particularly preferably 40 mg/L or less.
  • the microorganisms can be suitably cultured, and by setting the content to the upper limit or less, the microorganisms were not consumed. There is an advantage that the medium is not contaminated by various nutrient sources.
  • Examples of the sulfur compound generally include sulfur dioxide, CS 2 , COS, and H 2 S.
  • H 2 S and sulfur dioxide are preferable because they are easily consumed as nutrient sources for microorganisms. Therefore, it is more preferable that the synthesis gas contains the sum of H 2 S and sulfur dioxide in the above range.
  • phosphorus compound phosphoric acid is preferable because it can be easily consumed as a nutrient source for microorganisms. Therefore, it is more preferable that the synthesis gas contains phosphoric acid in the above range.
  • the nitrogen compound examples include nitric oxide, nitrogen dioxide, acrylonitrile, acetonitrile, HCN and the like, and HCN is preferable because it can be easily consumed as a nutrient source for microorganisms. Therefore, it is more preferable that the syngas contains HCN in the above range.
  • the synthesis gas may contain 0.01 mg/L or more and 90 mg/L or less of an aromatic compound, preferably 0.03 mg/L or more, more preferably 0.05 mg/L or more, and further preferably 0.1 mg/L. It is L or more and preferably 70 mg/L or less, more preferably 50 mg/L or less, and further preferably 30 mg/L or less.
  • the microbial fermentation step is a step of microbially fermenting the above-mentioned synthetic gas in a microbial fermentation tank to produce alcohol, particularly ethanol.
  • the microbial fermentation tank is preferably a continuous fermentation device.
  • the microbial fermenter can be used in any shape, and examples thereof include a stirring type, an airlift type, a bubble column type, a loop type, an open bond type, and a photobio type.
  • a known loop reactor having a main tank section and a reflux section can be preferably used. In this case, it is preferable to further include a circulation step of circulating the liquid medium between the main tank section and the reflux section.
  • the synthesis gas supplied to the microbial fermenter may be the gas obtained through the raw material gas production step as it is as long as the above-mentioned conditions for the components of the synthetic gas are satisfied, or impurities etc. can be reduced from the raw material gas.
  • the synthesis gas may be used after adding another predetermined gas to the removed gas.
  • another predetermined gas for example, at least one compound selected from the group consisting of sulfur compounds such as sulfur dioxide, phosphorus compounds, and nitrogen compounds may be added to form a synthesis gas.
  • the microbial fermenter may be continuously supplied with the synthetic gas and the microbial culture solution, but it is not necessary to supply the synthetic gas and the microbial culture solution at the same time.
  • Syngas may be supplied. It is known that certain anaerobic microorganisms produce alcohol, especially ethanol, etc. from a substrate gas such as synthesis gas by fermentation, and this type of gas-utilizing microorganism is cultured in a liquid medium. To be done. For example, a liquid medium and a gas-assimilating bacterium may be supplied and housed, and in this state, the synthetic gas may be supplied into the microbial fermentation tank while stirring the liquid medium. As a result, the gas-utilizing bacteria can be cultured in a liquid medium, and ethanol can be produced from the synthetic gas by the fermentation action.
  • the temperature of the medium or the like may be any temperature, but is preferably about 30 to 45°C, more preferably about 33 to 42°C, further preferably 36.5 to 37. It can be about 5°C.
  • the culture time is preferably 12 hours or longer in continuous culture, more preferably 7 days or longer, particularly preferably 30 days or longer, and most preferably 60 days or longer. From the viewpoint, it is preferably 720 days or less, more preferably 365 days or less.
  • the culture time means the time from the addition of the inoculum to the culture tank until the discharge of the entire culture solution from the culture tank.
  • the microorganism (seed) contained in the microorganism culture liquid is not particularly limited as long as it can produce ethanol by microbial fermentation of synthetic gas using carbon monoxide as a main raw material.
  • the microorganism (seed) is one that produces ethanol from the synthetic gas by the fermentation action of the gas-utilizing bacterium, and particularly a microorganism having a metabolic pathway of acetyl CoA.
  • the gas-utilizing bacteria the genus Clostridium is more preferable, and Clostridium autoethanogenum is particularly preferable, but the bacterium is not limited thereto. Further examples will be given below.
  • -Gas-utilizing bacteria include both eubacteria and archaebacteria.
  • the eubacterium include, for example, Clostridium genus bacteria, Moorella genus bacteria, Acetobacterium genus bacteria, Carboxydocella genus bacteria, Rhodopseudomonas genus bacteria, and Eubacterium.
  • Esubacterium Clostridium genus bacteria, Moorella genus bacteria, Acetobacterium genus bacteria, Carboxydocella genus bacteria, Rhodopseudomonas genus bacteria, and Eubacterium.
  • Eubacterium Clostridium genus bacteria
  • Moorella genus bacteria Acetobacterium genus bacteria
  • Carboxydocella genus bacteria Rhodopseudomonas genus bacteria
  • Eubacterium Eubacterium
  • Butyribacterium Butyribacterium
  • Oligotropha Oligotropha
  • Oxitropha genus bacterium
  • examples of archaea include Methanobacterium, Methanobrevibacter, Methanocalculus, Methanococcus, Methanosarcina, Methanosphaera, Methanothermobacter, Methanothrix, Methanoculleus, Methanofollis, Methanogenium.
  • Bacteria, Methanospirillium genus bacterium, Methanosaeta genus bacterium, Thermococcus genus bacterium, Thermofilum genus bacterium, Arcaheoglobus genus bacterium and the like can be mentioned.
  • Methanosarcina genus bacterium Methanococcus genus bacterium, Methanothermobacter genus bacterium, Methanothrix genus bacterium, Thermococcus genus bacterium, Thermofilum genus bacterium, Archaeoglobus genus bacterium are preferable.
  • Methanosarcina genus bacterium since the archaea are excellent in assimilating carbon monoxide and carbon dioxide, Methanosarcina genus bacterium, Methanothermobactor genus bacterium or Methanococcus genus bacterium is preferable, and Methanosarcina genus bacterium or Methanococcus genus bacterium is particularly preferable.
  • Specific examples of the bacterium of the genus Methanosarcina include Methanosarcina barkeri, Methanosarcina mazei, Methanosarcina acetivorans, and the like.
  • the target bacteria with high ethanol-producing ability are selected and used.
  • gas-utilizing bacteria with high ethanol-producing ability Clostridium autoethanogenum, Clostridium ljungdahlii, Clostridium aceticum, Clostridium carboxydivorance. , Moorella thermoacetica, Acetobacterium woodii, and the like.
  • Clostridium autoethanogenum is particularly preferable.
  • the medium used when culturing the above-mentioned microorganism is not particularly limited as long as it has a suitable composition according to the bacterium, and water as the main component and nutrients dissolved or dispersed in this water (for example, vitamins, And a phosphoric acid).
  • the composition of such a medium is adjusted so that the gas-utilizing bacteria can grow well.
  • Clostridium for the microorganism reference can be made to “0097” to “0099” and the like in US Patent Application Publication No. 2017/260552.
  • the alcohol-containing liquid obtained by the microbial fermentation process can be obtained as a suspension containing microorganisms, carcasses, proteins derived from microorganisms, and the like.
  • the protein concentration in the suspension varies depending on the type of microorganism, but is usually 30 to 1000 mg/L.
  • the protein concentration in the ethanol-containing liquid can be measured by the Kjeldahl method.
  • the alcohol-containing liquid obtained by the microbial fermentation process is then subjected to a separation process.
  • the ethanol-containing liquid is heated to room temperature to 500° C. under the condition of 0.01 to 1000 kPa (absolute pressure) to separate into a liquid or solid component containing microorganisms and a gas component containing ethanol. ..
  • the ethanol-containing liquid obtained by the microbial fermentation step was distilled and the desired ethanol was separated and purified, but since the ethanol-containing liquid contains microorganisms and proteins derived from microorganisms, etc.
  • the liquid is distilled as it is, foaming may occur in the distillation apparatus and continuous operation may be hindered. Further, it is known to use a membrane evaporator as a method for purifying an effervescent liquid, but the membrane evaporator has a low concentration efficiency and is not suitable for purifying a liquid containing a solid component.
  • the ethanol-containing liquid is heated to give a liquid or solid component containing microorganisms and a gas containing ethanol. The desired ethanol is separated and purified only from the separated gaseous component containing ethanol.
  • the present invention from the viewpoint of efficiently separating a liquid or solid component containing a microorganism, a carcass thereof, a protein derived from the microorganism, and the like, and a gas component containing ethanol, it is preferably under the condition of 10 to 200 kPa, more preferably Is under conditions of 50 to 150 kPa, more preferably under normal pressure, preferably at a temperature of 50 to 200° C., more preferably at a temperature of 80 to 180° C., further preferably at a temperature of 100 to 150° C. I do.
  • the heating time in the separation step is not particularly limited as long as the gas component can be obtained, but from the viewpoint of efficiency or economy, it is usually 5 seconds to 2 hours, preferably 5 seconds to 1 hour, and more preferably It is preferably 5 seconds to 30 minutes.
  • the separation step described above is not particularly limited as long as it is an apparatus capable of efficiently separating an ethanol-containing liquid into a liquid or solid component (microorganisms or carcasses, proteins derived from microorganisms, etc.) and a gas component (ethanol) by thermal energy.
  • a drying device such as a rotary dryer, a fluidized bed dryer, a vacuum dryer, a conduction heating dryer, etc.
  • a conduction heating type dryer examples include a drum type dryer and a disk type dryer.
  • the liquefaction step is a step of liquefying the gas component containing alcohol, particularly ethanol, obtained in the above separation step by condensation.
  • the apparatus used in the liquefaction process is not particularly limited, but it is preferable to use a heat exchanger, particularly a condenser (condenser).
  • the condenser include a water-cooled type, an air-cooled type, an evaporation type, and the like, and among them, the water-cooled type is preferable.
  • the condenser may have a single stage or a plurality of stages.
  • the liquefaction obtained by the liquefaction step does not contain the components contained in the ethanol-containing liquid such as microorganisms and carcasses and proteins derived from the microorganisms. It does not exclude that the protein is contained in it. Even when a protein is contained in the liquefaction product, its concentration is preferably 40 mg/L or less, more preferably 20 mg/L or less, further preferably 15 mg/L or less.
  • the heat of condensation of the gas component obtained by the condenser may be reused as a heat source in the purification process described later. By reusing the heat of condensation, ethanol can be produced efficiently and economically.
  • alcohol is refined from the liquefaction product obtained in the liquefaction process.
  • This production method varies depending on the alcohol, but is not particularly limited as long as the specific compound specified in the present invention is limited to a specific content.
  • the purification process in ethanol is described in detail below.
  • the ethanol-containing liquid obtained in the microbial fermentation step can be supplied to the purification step without going through the above-mentioned separation step when components such as microorganisms have already been removed.
  • the refining step is a step of separating the ethanol-containing liquid obtained in the liquefaction step into a distillate having an increased concentration of the desired ethanol and a bottom liquid having a reduced concentration of the desired ethanol.
  • the purification step described in the present specification may be performed to produce the ethanol specified in the present invention.
  • the apparatus used in the purification step is, for example, a distillation apparatus, a processing apparatus including a pervaporation membrane, a processing apparatus including a zeolite dehydration membrane, a processing apparatus for removing low boiling point substances having a lower boiling point than ethanol, a high boiling point having a higher boiling point than ethanol.
  • Examples thereof include a processing device that removes a substance and a processing device that includes an ion exchange membrane. These devices may be used alone or in combination of two or more. As the unit operation, heat distillation or membrane separation may be suitably used.
  • desired ethanol can be obtained as a distillate with high purity using a distillation apparatus.
  • the temperature inside the distiller during the distillation of ethanol is not particularly limited, but is preferably 100° C. or lower, more preferably about 70 to 95° C.
  • the separation of ethanol from other components, that is, the distillation of ethanol can be performed more reliably.
  • the difference in distillation temperature is preferably ⁇ 13°C, more preferably ⁇ 11°C.
  • the difference in distillation temperature allows more reliable separation from other components, that is, distillation of ethanol, and is preferable for producing ethanol specified in the present invention.
  • the ethanol-containing liquid may be in the form of an organosiloxane having a boiling point of 100° C. or lower (eg, 1,1,3,3-tetramethyldisiloxane, hexamethyldisiloxane, etc.). It is considered that Si is contained. A small amount of Si can be contained in ethanol obtained by distilling such ethanol by leaving organosiloxane having a boiling point close to that of ethanol. In the present invention, the Si content in ethanol contained in the distillate can be adjusted by adjusting the above-mentioned distillation conditions. As a result, the Si content in the final ethanol can be adjusted. In the separation step, the temperature of gas introduced into the separation device is maintained at 20 to 40° C. to stabilize the organosiloxane in the synthesis gas, thereby adjusting the final Si content in ethanol. Can also
  • distillation apparatus It is preferable to use a plurality of distillation columns as the above-mentioned distillation apparatus. At that time, it is preferable to use a processing device including an ion exchange membrane between the distillation columns.
  • concentration of sodium ions and potassium ions is controlled by passing through the ion exchange membrane, whereby the sodium content and potassium content in the final ethanol can be adjusted to a suitable range.
  • the ethanol-containing liquid includes an aliphatic hydrocarbon having a boiling point higher than that of ethanol (eg, heptane, octane, decane, dodecane, tetradecane, etc.), an aromatic compound (eg, toluene, ethylbenzene, xylene, etc.), a dialkyl ether (eg, , Dibutyl ether, dipentyl ether, etc.).
  • the temperature of the uppermost part of the distillation column is raised to 5 to 10° C. or higher than usual to distill the aromatic compound,
  • the aromatic compound in ethanol contained in the distillate can be adjusted.
  • the content of aromatic compounds in the final ethanol can be adjusted.
  • the pressure in the distillation apparatus at the time of ethanol distillation may be atmospheric pressure, but is preferably less than atmospheric pressure, more preferably about 60 to 95 kPa (absolute pressure).
  • the yield of ethanol (the concentration of ethanol contained in the distillate after distillation) is preferably 90% by volume or more, more preferably 95% by volume or more.
  • a known separation membrane can be appropriately used, and for example, a zeolite membrane can be preferably used.
  • the concentration of ethanol contained in the distillate separated in the purification step is preferably 20% by volume to 99.99% by volume, more preferably 60% by volume to 99.9% by volume.
  • the concentration of ethanol contained in the bottom solution is preferably 0.001% by volume to 10% by volume, and more preferably 0.01% by volume to 5% by volume.
  • the bottom liquid separated in the purification process does not substantially contain nitrogen compounds.
  • “substantially free” does not mean that the concentration of the nitrogen compound is 0 mg/L, and the bottom liquid obtained in the refining process does not require the wastewater treatment process. It means that the concentration of the nitrogen compound is.
  • the desired ethanol is not purified from the ethanol-containing solution obtained in the microbial fermentation step, but the ethanol-containing solution is a liquid or solid component containing microorganisms and a gas component containing ethanol as described above. To separate. At that time, since the nitrogen compound remains on the side of the liquid or solid component containing the microorganism, the gas component containing ethanol contains almost no nitrogen compound.
  • the bottom product obtained when purifying ethanol from a liquefied product obtained by liquefying a gas component does not substantially contain a nitrogen compound.
  • the concentration of the nitrogen compound is 0.1 to 200 mg/L, preferably 0.1 to 100 mg/L, more preferably 0.1 to 50 mg/L. is there.
  • the bottom liquid separated in the refining process does not substantially contain phosphorus compounds.
  • the term "substantially free from” does not mean that the concentration of the phosphorus compound is 0 mg/L, and the bottom liquid obtained in the purification step does not require the wastewater treatment step. Means concentration. Even when the bottom product is contained in the phosphorus compound, the concentration of the phosphorus compound is 0.1 to 100 mg/L, preferably 0.1 to 50 mg/L, more preferably 0.1 to 25 mg/L. is there.
  • the bottoms discharged in the ethanol purification step are substantially free of nitrogen compounds and phosphorus compounds, and almost free of other organic substances. Therefore, it is possible to simplify the conventionally required wastewater treatment process.
  • the bottoms liquid separated in the refining process may be supplied to the wastewater treatment process.
  • organic substances such as nitrogen compounds and phosphorus compounds can be further removed from the bottom liquid.
  • the organic matter may be removed by anaerobically or aerobically treating the bottoms.
  • the removed organic matter may be used as a fuel (heat source) in the refining process.
  • the treatment temperature in the wastewater treatment step is usually 0 to 90°C, preferably 20 to 40°C, more preferably 30 to 40°C.
  • the waste liquor treatment etc. is more effective than the bottom liquor obtained by directly supplying the microbial fermentation step to the purification step. The load is reduced.
  • the concentration of the nitrogen compound in the treated liquid obtained by treating the bottom liquid is preferably 0.1 to 30 mg/L, more preferably 0.1 to 20 mg/L, and further preferably 0.1. It is ⁇ 10 mg/L, and it is particularly preferable that no nitrogen compound is contained.
  • the phosphorus compound concentration in the treatment liquid is preferably 0.1 to 10 mg/L, more preferably 0.1 to 5 mg/L, further preferably 0.1 to 1 mg/L. It is particularly preferred that no phosphorus compound is included.
  • Butadiene is a raw material of synthetic rubber, which is mainly produced by refining a C4 fraction produced as a by-product when synthesizing ethylene from petroleum (that is, naphtha cracking).
  • ethanol derived from fossil fuel
  • 1,3-butadiene in place of chemical industrial raw materials obtained from petroleum.
  • a method for synthesizing butadiene using ethanol derived from such microbial fermentation a method using MgO as a catalyst, a method using a mixture of Al 2 O 3 and ZnO, a catalyst having a magnesium silicate structure, etc. are known. ing.
  • hafnium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, gallium, niobium, silver, indium, cerium and the like are used as the catalyst.
  • 1,3-butadiene By bringing the ethanol of the present invention into contact with the above-mentioned catalyst and heating, an ethanol conversion reaction occurs, and 1,3-butadiene can be synthesized.
  • 1,3-butadiene By synthesizing 1,3-butadiene using ethanol of the present invention as a raw material, it becomes possible to realize an ultimate resource recycling society that does not depend on petroleum resources.
  • the heating temperature for proceeding the conversion reaction is such that the temperature in the reaction system is, for example, 200 to 450° C., preferably 300 to 400° C. If the temperature in the reaction system is lower than the above range, sufficient catalytic activity may not be obtained, the reaction rate may decrease, and the production efficiency may decrease. On the other hand, if the temperature in the reaction system exceeds the above range, the catalyst may be easily deteriorated.
  • the reaction can be performed by a conventional method such as a batch system, a semi-batch system, or a continuous system.
  • a conventional method such as a batch system, a semi-batch system, or a continuous system.
  • the conversion rate of ethanol can be increased, but with the ethanol according to the present invention, even if the continuous system is adopted, the ethanol can be converted more efficiently than in the conventional case. can do.
  • ethanol derived from a recyclable resource having a gas containing carbon monoxide and hydrogen as a substrate such as that of the present invention, is a fossil fuel-derived ethanol in a gas chromatograph measured by gas chromatography-mass spectrometry It is thought that this is due to the presence of a unique peak that is not found in ethanol of.
  • a suspension bed system for example, a suspension bed system, a fluidized bed system, a fixed bed system, etc.
  • a gas phase method or a liquid phase method may be used.
  • a fixed-bed gas-phase continuous flow reactor for filling the above-mentioned catalyst into a reaction tube to form a catalyst layer and allowing the raw materials to flow as a gas and react in the gas phase in terms of easy recovery and regeneration of the catalyst. It is preferable to use.
  • the ethanol of the present invention may be gasified and supplied to the reactor without being diluted, or may be appropriately diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide or the like into the reactor. May be supplied.
  • an inert gas such as nitrogen, helium, argon, carbon dioxide or the like into the reactor. May be supplied.
  • reaction product (1,3-butadiene) is separated by gas-liquid separation at 10° C., and only the gas is extracted, a method of contacting with a drying material such as calcium chloride and molecular sieves, Separation and purification can be carried out by a separation means such as filtration, concentration, distillation, extraction or a combination of these.
  • the purity of the obtained butadiene is preferably 70% or higher, more preferably 75% or higher, even more preferably 80% or higher, even more preferably 82% or higher. This is because the yield of the polymerization reaction is improved.
  • the purity of butadiene can be calculated by the following formula.
  • Butadiene Purity Butadiene Concentration/Total Organic Compound Purity
  • the ratio between the concentration of the obtained butadiene and the concentration of the oxygen-containing compound is preferably 3 or more. This is to prevent deactivation of the catalyst used in the polymerization reaction.
  • the ratio between the concentration of butadiene and the concentration of oxygen-containing compound can be calculated by the following formula.
  • Butadiene/oxygenated compound butadiene concentration/(ethanol concentration + acetaldehyde concentration + acetic acid concentration + ethyl acetate concentration + diethyl ether concentration)
  • the ratio of the concentration of the obtained butadiene and the concentration of the hydrocarbon compound is preferably 5 or more. This is to increase the purity of the polymer.
  • the ratio between the concentration of butadiene and the concentration of hydrocarbon compound can be calculated by the following formula.
  • Butadiene/hydrocarbon compound butadiene concentration/(ethylene concentration + butene concentration + propylene concentration + butane concentration)
  • the method for producing the conjugated diene-based polymer of the present invention is A non-petrified raw material-derived alcohol having an iron content of 0.0001 mg/L or more and 2 mg/L or less is used as a raw material, and the alcohol is brought into contact with the catalyst and heated to give a conjugate having a carbon number of C 4 to C 12.
  • the raw material used in the step of producing the conjugated diene is not particularly limited as long as it is a non-petrified raw material-derived alcohol having an iron content of 0.0001 mg/L or more and 2 mg/L or less, and for example, the above-mentioned ethanol is used. You can
  • Examples of the conjugated diene having a carbon number of C 4 to C 12 obtained in the process for producing a conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene. , 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Of these, 1,3-butadiene is preferable.
  • These conjugated dienes may be used alone or in combination of two or more in the process of producing the non-petrification derived conjugated diene polymer.
  • a conjugated diene having a carbon number of C 4 to C 12 may be used, or an aromatic hydrocarbon other than the conjugated diene may be used.
  • Aromatic hydrocarbons used as monomers include styrene, methylstyrene, ethylstyrene, t-butylstyrene, ⁇ -methylstyrene, ⁇ -methyl-p-methylstyrene, chlorostyrene, bromostyrene, methoxystyrene, dimethylamino.
  • styrene examples thereof include methylstyrene, dimethylaminoethylstyrene, diethylaminomethylstyrene, diethylaminoethylstyrene, cyanoethylstyrene and vinylnaphthalene. Of these, styrene is preferred.
  • the method for polymerizing the monomer is not particularly limited, and the polymerization can be performed by a conventionally known method.
  • the polymerization method may be emulsion polymerization or solution polymerization.
  • Emulsion polymerization is performed by mixing a conventionally known solvent such as water with a hardly soluble monomer and an emulsifier (surfactant) in the solvent, and further adding a polymerization initiator soluble in the solvent to carry out the polymerization. Is the way.
  • the solution polymerization is a method in which a monomer and a polymerization initiator are added to an inert solvent to carry out polymerization.
  • the surfactant used in the process for producing the conjugated diene polymer is not particularly limited as long as it is one that is usually used in emulsion polymerization.
  • a specific example of the surfactant for example, a cationic surfactant or an anionic surfactant can be used.
  • the catalyst is not particularly limited, and a conventionally known catalyst can be used.
  • a catalyst containing a rare earth element-containing compound it is preferable to use a catalyst containing a rare earth element-containing compound, a coordination catalyst using a metallocene catalyst, or an anionic polymerization catalyst using an organometallic compound.
  • the inert solvent used in the step of producing the conjugated diene polymer is one that is usually used in solution polymerization and is not particularly limited as long as it does not inhibit the polymerization reaction.
  • Specific examples of the inert solvent include chain aliphatic hydrocarbons such as butane, pentane, hexane and heptane; alicyclic hydrocarbons such as cyclopentane and cyclohexane; aromatic hydrocarbons such as benzene, toluene and xylene; and the like. Are listed. These inert solvents may be used alone or in combination of two or more.
  • the polymerization initiator used in the step of producing the conjugated diene polymer is not particularly limited as long as it can polymerize a monomer containing a conjugated diene having a carbon number of C 4 to C 12 .
  • Specific examples thereof include a polymerization initiator having an organic alkali metal compound, an organic alkaline earth metal compound, a lanthanum series metal compound or the like as a main catalyst.
  • organic alkali metal compound examples include organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium; dilithiomethane, 1,4-dilithiobutane, 1,4 -Organic polyvalent lithium compounds such as dilithio-2-ethylcyclohexane, 1,3,5-trilithiobenzene, and 1,3,5-tris(lithiomethyl)benzene; Organic sodium compounds such as sodium naphthalene; Organic compounds such as potassium naphthalene Potassium compounds; and the like.
  • organic monolithium compounds such as n-butyllithium, sec-butyllithium, t-butyllithium, hexyllithium, phenyllithium and stilbenelithium
  • dilithiomethane 1,4-dilithiobutane
  • organic alkaline earth metal compound examples include di-n-butylmagnesium, di-n-hexylmagnesium, diethoxycalcium, calcium distearate, di-t-butoxystrontium, diethoxybarium and diisopropoxybarium.
  • Examples of the polymerization initiator having a lanthanum series metal compound as a main catalyst include lanthanum series metals such as lanthanum series metals such as lanthanum, cerium, praseodymium, neodymium, samarium and gadolinium, carboxylic acids, and phosphorus-containing organic acids And the like, and a polymerization initiator comprising a salt thereof as a main catalyst and a cocatalyst such as an alkylaluminum compound, an organic aluminum hydride compound, and an organic aluminum halide compound.
  • lanthanum series metals such as lanthanum series metals such as lanthanum, cerium, praseodymium, neodymium, samarium and gadolinium, carboxylic acids, and phosphorus-containing organic acids And the like
  • a polymerization initiator comprising a salt thereof as a main catalyst and a cocatalyst such as an alkylalumin
  • organic monolithium compounds and organic polyvalent lithium compounds are preferably used, organic monolithium compounds are more preferably used, and n-butyllithium is particularly preferably used.
  • the organic alkali metal compound is used as an organic alkali metal amide compound by previously reacting with a secondary amine compound such as dibutylamine, dihexylamine, dibenzylamine, pyrrolidine, piperidine, hexamethyleneimine, and heptamethyleneimine. You may.
  • the organic alkali metal amide compound as the polymerization initiator, the obtained rubber cross-linked product can be made more excellent in low exothermic property and wet grip property.
  • These polymerization initiators may be used alone or in combination of two or more.
  • the amount of the polymerization initiator used may be determined according to the molecular weight of the target conjugated diene polymer, but is usually 1 to 50 mmol, preferably 1.5 to 20 mmol, and more preferably 1000 g of the monomer. Is in the range of 2 to 15 mmol.
  • the polymerization temperature is usually in the range of -80 to +150°C, preferably 0 to 100°C, more preferably 30 to 90°C.
  • the polymerization mode any of batch mode, continuous mode and the like can be adopted.
  • a conjugated diene compound and an aromatic vinyl compound are copolymerized, a conjugated diene monomer unit and an aromatic vinyl monomer are used.
  • the batch method is preferable because it is easy to control the randomness of the bond with the unit.
  • conjugated diene-based polymer obtained by the production method of the present invention examples include isoprene rubber (IR), butadiene rubber (BR), styrene butadiene rubber (SBR), chloroprene rubber (CR), and acrylonitrile butadiene rubber (NBR). Can be mentioned. Among these, styrene-butadiene rubber is preferable as the rubber component used for the tire.
  • the weight average molecular weight (Mw) of the conjugated diene polymer obtained by the production method of the present invention is not particularly limited, but is 100,000 to 2,000,000 as a value measured by gel permeation chromatography in terms of polystyrene. Is preferred, 150,000 to 1,500,000 is more preferred, and 200,000 to 1,000,000 is particularly preferred.
  • Mw weight average molecular weight
  • the molecular weight distribution represented by the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the conjugated diene polymer obtained by the production method of the present invention is not particularly limited, but is preferably 4 It is from 0.0 to 6.0, and more preferably from 4.7 to 6.0.
  • Mw/Mn molecular weight distribution of the conjugated diene-based polymer
  • the glass transition temperature (Tg) of the conjugated diene polymer obtained by the production method of the present invention is not particularly limited, but is preferably ⁇ 40° C. to ⁇ 50° C., more preferably ⁇ 41° C. to ⁇ 47° C. is there.
  • the glass transition temperature of the conjugated diene-based polymer obtained by the production method of the present invention for example, by changing the blending ratio of the conjugated diene monomer and the aromatic hydrocarbon monomer in the conjugated diene-based polymer, It can be adjusted.
  • the conjugated diene-based polymer thus obtained by the production method of the present invention can be suitably used for various purposes after adding a filler, a crosslinking agent and the like.
  • silica when blended as a filler, it is possible to obtain a rubber composition capable of giving a rubber crosslinked product excellent in low heat buildup and wet grip properties.
  • the rubber composition of the present invention contains, as a rubber component, the conjugated diene polymer obtained by the above-described production method of the present invention and a filler.
  • the filler is not particularly limited, and examples thereof include silica, carbon black, calcium carbonate, talc and the like.
  • silica to be added to the rubber composition examples include dry method white carbon, wet method white carbon, colloidal silica, and precipitated silica.
  • wet-process white carbon containing hydrous silicic acid as a main component is preferable.
  • a carbon-silica dual phase filler in which silica is supported on the surface of carbon black may be used.
  • These silicas can be used alone or in combination of two or more.
  • the nitrogen adsorption specific surface area (measured by the BET method according to ASTM D3037-81) of silica used is preferably 50 to 300 m 2 /g, more preferably 80 to 220 m 2 /g.
  • the pH of silica is preferably pH 5-10.
  • the content of silica in the rubber composition is 10 to 200 parts by weight, preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition. ..
  • the content of silica in the above range is 10 to 200 parts by weight, preferably 30 to 150 parts by weight, and more preferably 50 to 100 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition. ..
  • the method of adding silica to the rubber composition is not particularly limited, and a method of adding and kneading to a solid conjugated diene-based polymer (dry kneading method) or a solution containing a conjugated diene-based polymer It is possible to apply a method (wet kneading method) or the like of adding to and solidifying and drying.
  • the carbon black blended in the rubber composition is not particularly limited, and examples thereof include furnace black, acetylene black, thermal black, channel black, and graphite.
  • the addition of carbon black imparts reinforcing properties, and in particular, can improve wear resistance.
  • a silane coupling agent may be further added to the rubber composition of the present invention from the viewpoint of further improving low heat buildup.
  • the silane coupling agent is not particularly limited, and various silane coupling agents can be used.
  • any silane coupling agent which has been conventionally used in combination with silica in the rubber industry can be used, and examples thereof include bis(3-triethoxysilylpropyl)tetrasulfide and bis(2-tritriene).
  • the rubber composition preferably further contains a crosslinking agent.
  • the cross-linking agent include sulfur, sulfur halides, organic peroxides, quinone dioximes, organic polyvalent amine compounds, and methylphenol group-containing alkylphenol resins. Among these, sulfur is preferably used.
  • the compounding amount of the crosslinking agent is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 4 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition. Is.
  • the rubber composition may be blended with a necessary amount of a compounding agent such as a crosslinking accelerator, a crosslinking activator, an antiaging agent, an activator, a process oil, a plasticizer, and a lubricant according to a conventional method. ..
  • a compounding agent such as a crosslinking accelerator, a crosslinking activator, an antiaging agent, an activator, a process oil, a plasticizer, and a lubricant according to a conventional method. ..
  • crosslinking accelerator When sulfur or a sulfur-containing compound is used as the crosslinking agent, it is preferable to use a crosslinking accelerator and a crosslinking activator together.
  • the crosslinking accelerator include sulfenamide-based crosslinking accelerators; guanidine-based crosslinking accelerators; thiourea-based crosslinking accelerators; thiazole-based crosslinking accelerators; thiuram-based crosslinking accelerators; dithiocarbamic acid-based crosslinking accelerators; xanthogenic acid-based accelerators.
  • Crosslinking accelerator and the like.
  • those containing a sulfenamide crosslinking accelerator are preferable.
  • These crosslinking accelerators may be used alone or in combination of two or more.
  • the amount of the crosslinking accelerator compounded is preferably 0.1 to 15 parts by weight, more preferably 0.5 to 5 parts by weight, and particularly preferably 1 to 4 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition. It is a department.
  • cross-linking activator examples include higher fatty acids such as stearic acid; zinc oxide; and the like. These cross-linking activators may be used alone or in combination of two or more.
  • the compounding amount of the crosslinking activator is preferably 0.05 to 20 parts by weight, particularly preferably 0.5 to 15 parts by weight, based on 100 parts by weight of the rubber component in the rubber composition.
  • the rubber composition of the present invention may contain a resin in addition to the rubber component.
  • a resin By compounding the resin, it is possible to impart tackiness to the rubber composition and to enhance the dispersibility of the filler in the rubber composition. As a result, the obtained rubber cross-linked product can be expected to have improved wet grip properties and abrasion resistance. Further, it is possible to improve the processability of the rubber composition as the same effect as the plasticizer.
  • the resin include C5 petroleum resin, C5/C9 petroleum resin, C9 petroleum resin, dicyclopentadiene resin, terpene resin, terpene phenol resin, aromatic modified terpene resin, alkylphenol-acetylene resin, rosin resin.
  • Resin Resin, rosin ester resin, indene resin, C9 resin containing indene, ⁇ -methylstyrene/indene copolymer resin, coumarone-indene resin, farnesene resin, polylimonene resin, etc. may be mentioned. These resins may be modified or hydrogenated. These resins may be used alone or in combination of two or more. The amount of the resin compounded is preferably 25 parts by weight or less with respect to 100 parts by weight of the rubber component in the rubber composition.
  • each component may be kneaded according to a conventional method, for example, by a compounding agent excluding heat-labile components such as a crosslinking agent and a crosslinking accelerator and the production method of the present invention
  • a heat-unstable component such as a crosslinking agent or a crosslinking accelerator
  • the kneading temperature of the compounding agent excluding heat-labile components and the rubber component containing the conjugated diene polymer obtained by the production method of the present invention is preferably 80 to 200°C, more preferably 120 to 180°C.
  • the kneading time is preferably 30 seconds to 30 minutes.
  • the kneaded product and the heat-unstable component are mixed after cooling to usually 100°C or lower, preferably 80°C or lower.
  • the rubber cross-linked product of the present invention is obtained by cross-linking (vulcanizing) the above-mentioned rubber composition of the present invention.
  • the rubber cross-linked product uses the rubber composition of the present invention, for example, is molded by a molding machine corresponding to a desired shape, for example, an extruder, an injection molding machine, a compressor, a roll, etc., and is cross-linked by heating. And fixing the shape as a crosslinked product.
  • the molding may be performed in advance and then crosslinked, or the molding and the crosslinking may be performed simultaneously.
  • the molding temperature is usually 10 to 200°C, preferably 25 to 120°C.
  • the crosslinking temperature is usually 100 to 200° C., preferably 130 to 190° C.
  • the crosslinking time is usually 1 minute to 24 hours, preferably 2 minutes to 12 hours, particularly preferably 3 minutes to 6 hours. ..
  • a general method used for crosslinking rubber such as press heating, steam heating, oven heating, and hot air heating may be appropriately selected.
  • the rubber cross-linked product of the present invention thus obtained is obtained by using the conjugated diene polymer obtained by the above-mentioned production method of the present invention, and therefore is excellent in low heat buildup and wet grip properties. And can be suitably used for tires.
  • a rubber cross-linked product takes advantage of such characteristics, and in tires, materials for various parts of the tire such as cap treads, base treads, carcass, sidewalls and beads; hoses, belts, mats, anti-vibration rubber, It can be used for various purposes such as materials for various industrial products; resin impact resistance improvers; resin film buffers; shoe soles; rubber shoes; golf balls; toys.
  • the rubber cross-linked product of the present invention can be suitably used for tire parts such as treads, carcasses, sidewalls, and bead parts in various tires such as all-season tires, high-performance tires, and studless tires. Since it is particularly excellent in low heat buildup, it can be used particularly suitably for a tread of a fuel efficient tire.
  • ⁇ Method for quantifying 1,3-butadiene Quantitative evaluation of 1,3-butadiene was conducted by analysis using a gas chromatography device (GC-2014, manufactured by SHIMADZU). The measurement conditions were as follows. ⁇ GC/MS analysis conditions> Column: Rt-Q-BOND (length 30 m, inner diameter 0.32 mm, film thickness 10 ⁇ m) Oven temperature: 60°C, 11.5 minutes ⁇ 10°C/min ⁇ 100°C, 14.5 minutes ⁇ 10°C/min ⁇ 250°C Sampling time: 5 minutes Carrier gas: He (30 cm/s) Split ratio: 75
  • Ethanol was produced as follows. (Raw material gas generation process) The gas discharged after burning general waste in a refuse incineration facility was used. The components of the source gas were about 30% by volume of carbon monoxide, about 30% by volume of carbon dioxide, about 30% by volume of hydrogen and about 10% by volume of nitrogen.
  • the ethanol-containing liquid was introduced into a distillation apparatus equipped with a heater using steam at 170°C. After raising the temperature of the bottom of the distillation column to 101° C. within 8 to 15 minutes, the above-mentioned ethanol-containing liquid was introduced from the middle of the distillation column, and during continuous operation, the bottom of the column was 101° C., the middle of the column was 99° C., The top part was continuously operated at 91° C. under the condition of 15 seconds/L to obtain purified ethanol. The content of iron in the obtained ethanol was 0.1 mg/L and the content of Si was 50 mg/L.
  • the content of toluene in the obtained ethanol was 0.07 mg/L, the content of ethylbenzene was 0.8 mg/L, and the total content of m-xylene and p-xylene was 0.2 mg/L. ..
  • the content of n-hexane in the obtained ethanol was 0.1 mg/L, the content of n-heptane was 0.04 mg/L, the content of n-octane was 0.02 mg/L, the content of n-decane.
  • the amount was 0.32 mg/L, the content of n-dodecane was 0.1 mg/L, and the content of tetradecane was 0.03 mg/L.
  • the content of dibutyl ether in the obtained ethanol was 20 mg/L.
  • 1,3-Butadiene 1,3-Butadiene was produced using the ethanol obtained as described above.
  • the ethanol obtained was passed through a single tube heated to 90° C. to be vaporized in order to use it as a gas to be subjected to the reaction, and the vaporized ethanol gas was combined with nitrogen.
  • the flow rate of ethanol gas was SV 360 L/hr/L, and nitrogen was controlled to be SV 840 L/hr/L by mass flow control, so that 30% by volume of ethanol (gas conversion) and 70% by volume of nitrogen (gas conversion) were obtained.
  • a mixed gas was used.
  • a stainless steel having a diameter of 1/2 inch (1.27 cm) and a length of 15.7 inches (40 cm) filled with 0.85 g of a 1,3-butadiene synthesis catalyst containing Hf and Zn as main components.
  • a 1,3-butadiene-containing gas was obtained by continuously supplying the above mixed gas while maintaining the temperature of the cylindrical reaction tube at 325° C. and the pressure (pressure of the reaction bed) at 0.1 MPa.
  • the content of 1,3-butadiene in the obtained 1,3-butadiene-containing gas was quantified using a gas chromatograph of GC-2014 (manufactured by SHIMADZU). The results are as shown in Table 1.
  • the content of toluene in the obtained ethanol is unmeasurable (below the detection limit, less than 0.01 mg/L), and the content of ethylbenzene is not measurable (below the detection limit, less than 0.1 mg/L). However, the total content of m-xylene and p-xylene was unmeasurable (below the detection limit, less than 0.2 mg/L).
  • the content of toluene in the obtained ethanol is unmeasurable (below the detection limit, less than 0.01 mg/L), and the content of ethylbenzene is not measurable (below the detection limit, less than 0.1 mg/L). However, the total content of m-xylene and p-xylene was unmeasurable (below the detection limit, less than 0.2 mg/L).
  • ethanol produced using the gas discharged after burning general waste in a refuse incineration facility is compared to conventional fossil fuel-derived ethanol and plant saccharification and fermentation-derived ethanol. It was found that the conversion efficiency to 1,3-butadiene was high.
  • SBR evaluation method The styrene-butadiene rubber (SBR) synthesized below was evaluated by the following method. ⁇ Average molecular weight and polydispersity The number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined by GPC measurement using a column of Shodex GPC KF-806L (manufactured by Showa Denko KK) in HLC-8420GPC (manufactured by Tosoh Corporation). A solution having a sample concentration of 0.2 w/v% was prepared by using THF as an eluent and polystyrene as a standard substance. 100 ⁇ L of the adjusted sample was injected at a flow rate of 1.0 mL/min.
  • the column temperature was 40°C.
  • the dispersity was calculated by Mw/Mn.
  • ⁇ Glass transition temperature (Tg) Using a thermal analyzer EXSTAR DSC7020 (manufactured by Hitachi High-Tech Science), the glass transition temperature was measured under a nitrogen atmosphere at a temperature range of ⁇ 100 to 100° C. and a heating rate of 20° C./min.
  • Mw/Mn falls within the range of 4.7 to 6.0 when the iron content of ethanol is in the range of 0.0001 to 2 mg/L.
  • iron is present in ethanol in the range of 0.0001 to 2 mg/L, a small amount of oxygen can be adsorbed, a side reaction during butadiene synthesis can be prevented, and the progress of polymerization reaction can be prevented, thereby improving the selectivity of butadiene. ..
  • the ratio of styrene and butadiene can be precisely controlled, and Mw/Mn can fall within the range of 4.7 to 6.0.
  • the polymerization yield is high when the iron content of ethanol is in the range of 0.0001 to 2 mg/L. It is considered that when iron is present in ethanol in the range of 0.0001 to 2 mg/L, a small amount of oxygen mixed therein can be adsorbed, catalyst deactivation due to oxygen is prevented during emulsion polymerization, and the polymerization yield is increased. On the other hand, when 2 mg/L or more of iron is contained in ethanol, the amount of butane mixed in the produced butadiene gas increases in the course of the butadiene synthesis reaction. It is considered that the presence of butane, which does not affect the polymerization reaction during the emulsion polymerization, lowers the proportion of butadiene in the polymer and lowers the polymerization yield.
  • the glass transition temperature falls within the range of -41 to -47°C when the iron content of ethanol is in the range of 0.0001 to 2 mg/L.
  • the inclusion of iron in ethanol increases the amount of ethyl acetate mixed in the butadiene gas produced during the butadiene synthesis reaction. It is considered that the presence of ethyl acetate during the emulsion polymerization causes a part of the ethyl acetate to be taken into the rubber, which lowers the crystallinity of the molecule and lowers the glass transition temperature.

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